Investigation of long-term anti-sulfur and deactivation mechanism of monolithic Mn-Fe-Ce/Al2O3 catalysts for NH3-SCR: Changes in physicochemical and adsorption properties

Abstract

Owing to the different reaction properties and deactivation mechanisms caused by the structural discrepancy of monolithic catalysts, abundant scientific results of powder or granular NH3-SCR catalysts have still not sufficiently robustly applied in recent years. Furthermore, minimal research has been focused on monolithic catalysts. As a result, this work prepared monolithic Mn-Fe-Ce/Al2O3 catalysts by active component impregnation (ACI-Mn-Fe-Ce/Al2O3) and precursor impregnation methods (PI-Mn-Fe-Ce/Al2O3) and investigates the long-term SO2 and H2O resistance of the catalysts. Compared with the PI-Mn-Fe-Ce/Al2O3 catalyst, the monolithic ACI-Mn-Fe-Ce/Al2O3 catalyst showed better performance. The catalytic activity follows a bell-shaped curve with an optimal performance at a drug loading of 5 %. The ACI-Mn-Fe-Ce/Al2O3 catalyst exhibits long-term resistance to SO2 and H2O and can still convert more than 70 % NOx after 168 h of SO2 and H2O resistance test. Characterization of the ACI-Mn-Fe-Ce/Al2O3 catalysts before and after the reaction showed that the reducibility decreased after the reaction, and more Mn4+ was transformed into Mn2+ to weaken the catalytic activity. However, more Fe2+ and Ce3+ were generated during the reaction, increasing the number of oxygen vacancies, oxygen defects, and hydroxyl-like groups, all of which would contribute to a certain extent to counteract the passivation effect of SO2 on the catalysts. In situ DRIFTs analysis shows that the formation of surface sulfates has a minimal effect on the adsorption of NO, but it does affect the adsorption of coordinated NH3 on Lewis acid sites. This work elucidates the deactivation details of Mn-Fe-Ce/Al2O3 catalysts from the perspective of physicochemical properties, which provides a reference for the development of better low-temperature SO2-resistance catalysts for industrial applications.